Characterization of Polymers by Direct Pyrolysis/Chemical Ionization Mass Spectrometry

Abstract

Abstract The characterization of polymers by pyrolysis directly in the ion source of a double focusing magnetic sector mass spectrometer, operating in the chemical ionization mode, is described. Pyrolysis is achieved by two different probe techniques. A low temperature, slow heating rate direct insertion probe (DIP) is used at 400°C, and a specifically constructed high temperature, fast heating rate, high temperature pyrolysis (HTP) probe is used at 1000°C. This probe is capable of achieving pyrolysis temperatures of 1200°C at controlled heating rates up to 20,000°C/s. The mass spectrometric analysis of the pyrolysis products was achieved under chemical ionization (CI) conditions utilizing methane, isobutane, and ammonia as reagent gases. Under CI conditions the molecular ions formed in the mass spectrometer show little tendency to fragment. The CI mass pyrograms are very simple, with each peak in the spectra ascribable to a particular component in the pyrolysis product mixture. The results of the two probe pyrolysis techniques are compared and the utility of each technique for the characterization of polymers is demonstrated using the vinyl polymers polymethyl methacrylate, polyvinyl chloride, and polystyrene.